JP6983486B2 - Alginic acid-based nanofibers and their manufacturing methods - Google Patents
Alginic acid-based nanofibers and their manufacturing methods Download PDFInfo
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- 235000010443 alginic acid Nutrition 0.000 title claims description 86
- 229920000615 alginic acid Polymers 0.000 title claims description 86
- 150000004781 alginic acids Chemical class 0.000 title claims description 81
- 239000000783 alginic acid Substances 0.000 title claims description 78
- 229960001126 alginic acid Drugs 0.000 title claims description 78
- 239000002121 nanofiber Substances 0.000 title claims description 55
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 239000006185 dispersion Substances 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 14
- 239000011734 sodium Substances 0.000 claims description 14
- 229910052708 sodium Inorganic materials 0.000 claims description 14
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 13
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000011591 potassium Substances 0.000 claims description 8
- 229910052700 potassium Inorganic materials 0.000 claims description 8
- 238000001694 spray drying Methods 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims 1
- 239000007924 injection Substances 0.000 claims 1
- 229920001282 polysaccharide Polymers 0.000 description 25
- 239000005017 polysaccharide Substances 0.000 description 25
- 150000004804 polysaccharides Chemical class 0.000 description 25
- 239000002994 raw material Substances 0.000 description 13
- 239000002253 acid Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 238000001878 scanning electron micrograph Methods 0.000 description 9
- AEMOLEFTQBMNLQ-SYJWYVCOSA-N (2s,3s,4s,5s,6r)-3,4,5,6-tetrahydroxyoxane-2-carboxylic acid Chemical compound O[C@@H]1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@@H]1O AEMOLEFTQBMNLQ-SYJWYVCOSA-N 0.000 description 8
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 7
- 229940072056 alginate Drugs 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 5
- 235000010413 sodium alginate Nutrition 0.000 description 5
- 239000000661 sodium alginate Substances 0.000 description 5
- 229940005550 sodium alginate Drugs 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- 150000002772 monosaccharides Chemical class 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 235000010408 potassium alginate Nutrition 0.000 description 4
- 239000000737 potassium alginate Substances 0.000 description 4
- MZYRDLHIWXQJCQ-YZOKENDUSA-L potassium alginate Chemical compound [K+].[K+].O1[C@@H](C([O-])=O)[C@@H](OC)[C@H](O)[C@H](O)[C@@H]1O[C@@H]1[C@@H](C([O-])=O)O[C@@H](O)[C@@H](O)[C@H]1O MZYRDLHIWXQJCQ-YZOKENDUSA-L 0.000 description 4
- -1 propylene glycol ester Chemical class 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 241001474374 Blennius Species 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000010407 ammonium alginate Nutrition 0.000 description 3
- 239000000728 ammonium alginate Substances 0.000 description 3
- KPGABFJTMYCRHJ-YZOKENDUSA-N ammonium alginate Chemical compound [NH4+].[NH4+].O1[C@@H](C([O-])=O)[C@@H](OC)[C@H](O)[C@H](O)[C@@H]1O[C@@H]1[C@@H](C([O-])=O)O[C@@H](O)[C@@H](O)[C@H]1O KPGABFJTMYCRHJ-YZOKENDUSA-N 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 230000002522 swelling effect Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- HDSBZMRLPLPFLQ-UHFFFAOYSA-N Propylene glycol alginate Chemical compound OC1C(O)C(OC)OC(C(O)=O)C1OC1C(O)C(O)C(C)C(C(=O)OCC(C)O)O1 HDSBZMRLPLPFLQ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 235000010410 calcium alginate Nutrition 0.000 description 2
- 239000000648 calcium alginate Substances 0.000 description 2
- 229960002681 calcium alginate Drugs 0.000 description 2
- OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical compound [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 235000013373 food additive Nutrition 0.000 description 2
- 239000002778 food additive Substances 0.000 description 2
- 229930014626 natural product Natural products 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 235000010409 propane-1,2-diol alginate Nutrition 0.000 description 2
- 239000000770 propane-1,2-diol alginate Substances 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 0 C*[C@](C(*)O[C@](C)(C1(C)O)O*)C1(C)O Chemical compound C*[C@](C(*)O[C@](C)(C1(C)O)O*)C1(C)O 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical group 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 210000001156 gastric mucosa Anatomy 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 125000004436 sodium atom Chemical group 0.000 description 1
- 235000021023 sodium intake Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
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- Polysaccharides And Polysaccharide Derivatives (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、アルギン酸系ナノファイバー及びその製造方法に関する。 The present invention relates to alginic acid-based nanofibers and a method for producing the same.
アルギン酸は、主に海草類に含まれる多糖類の一種であり、α−Ｌ−グルロン酸、β−Ｄ−マンヌロン酸が直鎖状に共重合した構造を取っており、人工イクラ、ゲル化剤、増粘剤等の食品及び食品添加物、胃粘膜保護剤、歯科印象剤等の医薬品、紙のコーティング剤等の用途に利用されている。しかしながら、アルギン酸は水に不溶とされているため、通常、ナトリウム塩等の形で用いられる（非特許文献１）。 Alginic acid is a kind of polysaccharide mainly contained in seaweeds, and has a structure in which α-L-gluuronic acid and β-D-mannuronic acid are copolymerized in a linear manner. It is used for foods such as thickeners, food additives, gastric mucosa protective agents, pharmaceuticals such as dental impressionants, and paper coating agents. However, since alginic acid is insoluble in water, it is usually used in the form of a sodium salt or the like (Non-Patent Document 1).
アルギン酸をナトリウム塩として用いる場合、アルギン酸の含有量に比例して、ナトリウムの含有量も当然に増加する。しかしながら、食品及び食品添加物、又は医薬品の用途において用いられる場合、ナトリウムの摂取が問題となる可能性がある。また、工業用途として、例えば電子材料等の用途に用いる場合では、ナトリウム原子の含有が望ましくない場合がある。 When alginic acid is used as a sodium salt, the sodium content naturally increases in proportion to the alginic acid content. However, when used in food and food additives, or pharmaceutical applications, sodium intake can be problematic. In addition, when used for industrial purposes such as electronic materials, the inclusion of sodium atoms may not be desirable.
本発明は、アルギン酸系ナノファイバー及びその製造方法を提供することを課題とする。 An object of the present invention is to provide an alginic acid-based nanofiber and a method for producing the same.
また、金属含有量の低いアルギン酸系ナノファイバー及びその製造方法を提供することを課題とする。 Another object of the present invention is to provide alginic acid-based nanofibers having a low metal content and a method for producing the same.
上記背景のもと、本発明者等は、カルボン酸ナトリウム構造ではなく、カルボン酸構造であれば、ナトリウム等の金属原子の混入を避けることが可能であることに着目した。本発明者等は、前記課題を達成するため、この着眼点に基づき鋭意検討した結果、アルギン酸を用いて、短時間で、簡易に、安価な原料から均一で透明性の高いナノファイバー分散体を製造できることを見出し、本発明を完成するに至った。 Based on the above background, the present inventors have focused on the fact that it is possible to avoid contamination with metal atoms such as sodium if it has a carboxylic acid structure instead of a sodium carboxylate structure. As a result of diligent studies based on this point of view, the present inventors have made a uniform and highly transparent nanofiber dispersion from an inexpensive raw material in a short time and easily using alginic acid in order to achieve the above-mentioned problems. We have found that it can be manufactured, and have completed the present invention.
即ち、本発明は、以下の態様を包含する。 That is, the present invention includes the following aspects.
項１． β−Ｄ−マンヌロン酸構造及び／又はα−Ｌ−グルロン酸構造を有する多糖類を含むナノファイバー。 Item 1. Nanofibers containing polysaccharides having a β-D-mannuronic acid structure and / or an α-L-gluuronic acid structure.
項２． アルギン酸構造を有する多糖類を含むナノファイバー。 Item 2. Nanofibers containing polysaccharides with an alginic acid structure.
項３． ナトリウム、カリウムの含有量の和が、前記ナノファイバーの総重量に対して５重量％以下である前記項１又は２に記載のナノファイバー。 Item 3. Item 2. The nanofiber according to Item 1 or 2, wherein the sum of the contents of sodium and potassium is 5% by weight or less based on the total weight of the nanofiber.
項４． 前記多糖類がβ−Ｄ−マンヌロン酸及び／又はα−Ｌ−グルロン酸の重合体である、前記項１〜３のいずれかに記載のナノファイバー。 Item 4. Item 3. The nanofiber according to any one of Items 1 to 3, wherein the polysaccharide is a polymer of β-D-mannuronic acid and / or α-L-gluronic acid.
項５． 直径が１００ｎｍ以下である前記項１〜４のいずれかに記載のナノファイバー。 Item 5. Item 2. The nanofiber according to any one of Items 1 to 4, wherein the nanofiber has a diameter of 100 nm or less.
項６． アルギン酸及び／又はアルギン酸誘導体と水とを含む混合物に対して、５０ＭＰａ以上の高圧処理を行う工程を含む、アルギン酸及び／又はアルギン酸誘導体のナノファイバーを製造する方法。 Item 6. A method for producing nanofibers of alginic acid and / or alginic acid derivative, which comprises a step of subjecting a mixture containing alginic acid and / or alginic acid derivative and water to a high pressure treatment of 50 MPa or more.
項７． 固形分の総重量に対してのナトリウム含有量が５重量％以下である、前記項６に記載の製造方法。 Item 7. Item 6. The production method according to Item 6, wherein the sodium content with respect to the total weight of the solid content is 5% by weight or less.
項８． 固形分の総重量に対してアルギン酸の割合が５０重量％以上である、前記項６又は７に記載の製造方法。 Item 8. Item 6. The production method according to Item 6 or 7, wherein the ratio of alginic acid to the total weight of the solid content is 50% by weight or more.
項９． ｐＨ９以下で前記高圧処理を行う、前記項６〜８のいずれかに記載の製造方法。 Item 9. Item 6. The production method according to any one of Items 6 to 8, wherein the high pressure treatment is performed at a pH of 9 or less.
項１０． 前記項１〜５のいずれかに記載のナノファイバー及び水を８０重量％以上含む溶媒を含むナノファイバー分散体。 Item 10. Item 2. The nanofiber dispersion according to any one of Items 1 to 5 and containing a solvent containing 80% by weight or more of water.
項１１． 前記項１０に記載の分散体を噴霧乾燥して得られる、粒径（Ｄ５０）が２０μｍ以下の粒子。 Item 11. Particles having a particle size (D50) of 20 μm or less, obtained by spray-drying the dispersion according to Item 10.
本発明の方法によれば、簡易な装置を用いて、分散性及び分散液の透明性が高く、均一で他材料との親和性にも優れるアルギン酸系ナノファイバーとその製造方法を提供できる。また、水に不溶なアルギン酸を用いて、金属含有量の低いアルギン酸系ナノファイバーを提供できる。 According to the method of the present invention, it is possible to provide an alginic acid-based nanofiber having high dispersibility and transparency of the dispersion liquid, and having excellent compatibility with other materials, and a method for producing the same, by using a simple device. Further, alginic acid insoluble in water can be used to provide alginic acid-based nanofibers having a low metal content.
１．アルギン酸系ナノファイバー
本発明のナノファイバーは、β−Ｄ−マンヌロン酸構造及び／又はα−Ｌ−グルロン酸構造を有する多糖類を含むナノファイバーである。また、本発明のナノファイバーは、好ましくはアルギン酸構造を有する多糖類を含むナノファイバーである。本発明において、両者ともに「アルギン酸系ナノファイバー」ということもある。
1. 1. Alginic acid-based nanofibers The nanofibers of the present invention are nanofibers containing polysaccharides having a β-D-mannuronic acid structure and / or an α-L-gluuronic acid structure. Further, the nanofiber of the present invention is preferably a nanofiber containing a polysaccharide having an alginic acid structure. In the present invention, both may be referred to as "alginic acid-based nanofibers".
本発明のアルギン酸系ナノファイバーは、β−Ｄ−マンヌロン酸構造及び／又はα−Ｌ−グルロン酸構造（好ましくはアルギン酸構造）を有する多糖類を含むナノファイバーである。β−Ｄ−マンヌロン酸構造とは、好ましくは、下記構造式（１）： The alginic acid-based nanofiber of the present invention is a nanofiber containing a polysaccharide having a β-D-mannuronic acid structure and / or an α-L-gluuronic acid structure (preferably an alginic acid structure). The β-D-mannuronic acid structure is preferably the following structural formula (1):
で表わされる構造をいう。α−Ｌ−グルロン酸構造とは、好ましくは、下記構造式（２）： Refers to the structure represented by. The α-L-gluuronic acid structure is preferably the following structural formula (2):
で表わされる構造をいう。 Refers to the structure represented by.
アルギン酸構造とは、β−Ｄ−マンヌロン酸及びα−Ｌ−グルロン酸というカルボキシル基を有する単糖が直線上に結合したポリマー構造をいう。より具体的に言えば、前記構造式（１）のみからなるブロック、前記構造式（２）のみからなるブロック、並びに前記構造式（１）及び（２）の混合からなるブロックの３種のブロックによって組み立てられる構造をいう。 The alginic acid structure refers to a polymer structure in which monosaccharides having a carboxyl group, β-D-mannuronic acid and α-L-gluuronic acid, are linearly bonded. More specifically, there are three types of blocks: a block consisting of only the structural formula (1), a block consisting only of the structural formula (2), and a block consisting of a mixture of the structural formulas (1) and (2). Refers to the structure assembled by.
前記多糖類としては、前記構造式（１）及び前記構造式（２）以外の構造（例えば、前記構造式（１）及び（２）以外の単糖構造）を単量体構造として含んでいてもよい。その他の単量体構造としては、例えば、下記構造式（３）： The polysaccharide includes a structure other than the structural formulas (1) and the structural formula (2) (for example, a monosaccharide structure other than the structural formulas (1) and (2)) as a monomer structure. May be good. Examples of other monomer structures include the following structural formula (3):
（式中、Ｒはナトリウム、カリウム、アンモニウム、カルシウム、プロピレングリコールエステルを示す。）
で表わされるβ−Ｄ−マンヌロン酸系構造、下記構造式（４）：
(In the formula, R indicates sodium, potassium, ammonium, calcium, propylene glycol ester.)
Β-D-mannuronic acid system structure represented by, the following structural formula (4):
（式中、Ｒはナトリウム、カリウム、アンモニウム、カルシウム、プロピレングリコールエステルを示す。）
で表わされるα−Ｌ−グルロン酸系構造の単糖構造を挙げることができる。
(In the formula, R indicates sodium, potassium, ammonium, calcium, propylene glycol ester.)
Can be mentioned as a monosaccharide structure having an α-L-gluuronic acid-based structure represented by.
前記構造式（１）、（２）、（３）及び（４）の単量体構造は、多糖類全体に対する単量体構造の割合として、９５％以上であることが好ましく、９７〜１００％であることがより好ましい。特に好ましくは、前記多糖類は、実質的に（例えば、９９％以上）前記構造式（１）、前記構造式（２）、前記構造式（３）及び前記構造式（４）のみからなるアルギン酸又はその誘導体である。 The monomer structure of the structural formulas (1), (2), (3) and (4) preferably has a ratio of the monomer structure to the whole polysaccharide of 95% or more, preferably 97 to 100%. Is more preferable. Particularly preferably, the polysaccharide is alginic acid which is substantially (for example, 99% or more) composed of only the structural formula (1), the structural formula (2), the structural formula (3) and the structural formula (4). Or a derivative thereof.
前記アルギン酸又はその誘導体としては、アルギン酸、アルギン酸ナトリウム、アルギン酸カリウム、アルギン酸アンモニウム、アルギン酸カルシウム、アルギン酸エステル（例えば、アルギン酸プロピレングリコールエステル）等を挙げることができる。 Examples of the alginic acid or a derivative thereof include alginic acid, sodium alginate, potassium alginate, ammonium alginate, calcium alginate, alginic acid ester (for example, propylene glycol alginate) and the like.
前記多糖類は、多糖類総重量に対するナトリウム、カリウムの含有量の和が５重量％以下であることが好ましい。ナトリウム、カリウムの含有量は、ＩＣＰ発光分光分析法、蛍光Ｘ線分析（ＷＤＸ）、原子吸光分析、イオンクロマトグラフィ等により求めることができる。例えば、前記多糖類がアルギン酸又はアルギン酸の誘導体である場合、前記構造式（３）及び（４）におけるＲとして、ナトリウム及びカリウムが含まれる。ナトリウム含有量の多いアルギン酸ナトリウムは一般に水溶性であることが知られている。一方、ナトリウム含有量が低い（言い換えると、前記構造式（１）及び（２）の構造の割合が大きい）アルギン酸は、水への溶解性が極めて低い（例えば、ｐＨ２．５〜２．８の水へは不溶）ことが知られている。本発明では、アルギン酸等の非水溶性の多糖類であっても、ナノファイバーの成分として好ましく使用できる。 It is preferable that the sum of the contents of sodium and potassium with respect to the total weight of the polysaccharide is 5% by weight or less. The contents of sodium and potassium can be determined by ICP emission spectroscopic analysis, fluorescent X-ray analysis (WDX), atomic absorption spectrometry, ion chromatography and the like. For example, when the polysaccharide is alginic acid or a derivative of alginic acid, sodium and potassium are included as R in the structural formulas (3) and (4). Sodium alginate, which has a high sodium content, is generally known to be water-soluble. On the other hand, alginic acid having a low sodium content (in other words, a large proportion of the structures of the structural formulas (1) and (2)) has extremely low solubility in water (for example, pH 2.5 to 2.8). It is known to be insoluble in water). In the present invention, even a water-insoluble polysaccharide such as alginic acid can be preferably used as a component of nanofibers.
本発明のアルギン酸系ナノファイバーは、長くアスペクト比が大きい。例えば、得られるナノファイバーの直径（太さ）は好ましくは１００ｎｍ以下であり、より好ましくは１〜１００ｎｍであり、特に好ましくは１〜５０ｎｍである。長さは好ましくは１μｍ以上であり、より好ましくは１〜３０μｍである。アスペクト比は好ましくは２０以上であり、より好ましくは２０〜１０００である。ナノファイバーの長さ、太さ、アスペクト比は電子顕微鏡観察（ＳＥＭ、ＴＥＭ等）により測定することができる。 The alginic acid-based nanofibers of the present invention are long and have a large aspect ratio. For example, the diameter (thickness) of the obtained nanofibers is preferably 100 nm or less, more preferably 1 to 100 nm, and particularly preferably 1 to 50 nm. The length is preferably 1 μm or more, and more preferably 1 to 30 μm. The aspect ratio is preferably 20 or more, more preferably 20 to 1000. The length, thickness and aspect ratio of nanofibers can be measured by electron microscope observation (SEM, TEM, etc.).
２．アルギン酸系ナノファイバーの製造方法
本発明のアルギン酸系ナノファイバーは、原料である多糖類（好ましくはアルギン酸及び／又はアルギン酸誘導体）及び溶媒の混合物に対して５０ＭＰａ以上の高圧処理を行うことにより製造することができる。
2. 2. Method for Producing Alginic Acid-based Nanofibers The alginic acid-based nanofibers of the present invention shall be produced by subjecting a mixture of a raw material polysaccharide (preferably alginic acid and / or alginic acid derivative) and a solvent to a high pressure treatment of 50 MPa or more. Can be done.
本発明における高圧処理は、高圧をかけて噴射した混合物同士を衝突させる処理、高圧をかけて混合物を噴射して固体とぶつける処理等が考えられる。当該高圧処理としては、例えば、細いノズル（例えば、直径０．１〜０．２ｍｍ程度）から混合物を噴射する方法等が一般的である。混合物を噴射する際の圧力は５０ＭＰａ以上であり、好ましくは５０〜１０００ＭＰａ、より好ましくは１００〜７００ＭＰａである。 As the high-pressure treatment in the present invention, a treatment in which the mixtures injected by applying high pressure collide with each other, a treatment in which the mixture is injected by applying high pressure, and a process of colliding with a solid can be considered. As the high pressure treatment, for example, a method of injecting a mixture from a thin nozzle (for example, about 0.1 to 0.2 mm in diameter) is generally used. The pressure at the time of injecting the mixture is 50 MPa or more, preferably 50 to 1000 MPa, and more preferably 100 to 700 MPa.
前記高圧処理において、原料である多糖類（好ましくはアルギン酸又はその誘導体）は、種々の多糖類を使用することができる。例えば、一般的に海草類等の天然物から抽出されるアルギン酸及びその誘導体は、含まれる単糖類の比率が原料となる海草類の種類によって異なり、これら種々のアルギン酸及びその誘導体を使用することができる。アルギン酸又はその誘導体としては、水溶性のもの、膨潤性のもの、非膨潤性のもの等が知られているが、そのいずれも使用することができる。これらの多糖類は、一種単独であっても、二種以上混合で用いてもよい。アルギン酸の含有量は、アルギン酸及びアルギン酸の誘導体全量に対して５０重量％以上であることが好ましい。 In the high-pressure treatment, various polysaccharides can be used as the raw material polysaccharide (preferably alginic acid or a derivative thereof). For example, in the alginic acid and its derivatives generally extracted from natural products such as seaweeds, the ratio of monosaccharides contained thereof varies depending on the type of seaweeds as a raw material, and these various alginic acids and their derivatives can be used. As alginic acid or a derivative thereof, water-soluble ones, swellable ones, non-swellable ones and the like are known, and any of them can be used. These polysaccharides may be used alone or in a mixture of two or more. The content of alginic acid is preferably 50% by weight or more with respect to the total amount of alginic acid and alginic acid derivatives.
また、原料の多糖類（好ましくはアルギン酸又はその誘導体）は、天然物からの抽出以外にも、公知の方法により製造されたものを用いることも可能である。さらに、市販品をそのまま用いることも可能である。市販品としては、株式会社キミカ製のキミカアシッドＧ又はキミカアシッドＳＡ；和光純薬工業株式会社製のアルギン酸（膨潤性）又はアルギン酸（非膨潤性）等を挙げることができる。 Further, as the raw material polysaccharide (preferably alginic acid or a derivative thereof), it is also possible to use a polysaccharide produced by a known method in addition to extraction from a natural product. Further, it is also possible to use a commercially available product as it is. Examples of commercially available products include Kimika Acid G or Kimika Acid SA manufactured by Kimika Co., Ltd .; alginic acid (swellable) or alginic acid (non-swellable) manufactured by Wako Pure Chemical Industries, Ltd.
前記溶媒としては、多糖類（特にアルギン酸又はその誘導体）との親和性が高い点で、水を含むことが好ましい。溶媒には水以外に有機溶媒を含むことができるが、溶媒の総重量に対して、水の含有量が８０重量％以上（８０〜１００重量％）であることが好ましい。水以外の有機溶媒としては、アルコール等の極性溶媒が好ましい。 The solvent preferably contains water because of its high affinity with polysaccharides (particularly alginic acid or its derivatives). The solvent may contain an organic solvent in addition to water, but the water content is preferably 80% by weight or more (80 to 100% by weight) with respect to the total weight of the solvent. As the organic solvent other than water, a polar solvent such as alcohol is preferable.
前記多糖類（好ましくはアルギン酸又はその誘導体）及び溶媒の混合物は、多糖類が溶媒に溶解した溶液であっても、多糖類が溶媒に溶解していない分散液であってもよい。 The mixture of the polysaccharide (preferably alginic acid or a derivative thereof) and a solvent may be a solution in which the polysaccharide is dissolved in a solvent or a dispersion in which the polysaccharide is not dissolved in the solvent.
特に、アルギン酸又はその誘導体は、一般的に、水溶性のアルギン酸ナトリウム、アルギン酸カリウム、アルギン酸アンモニウム等が多く使用される。本発明では、これらの水溶性アルギン酸誘導体であっても原料として用いることが可能である。金属塩を含まないアルギン酸は、水酸化ナトリウム水溶液、水酸化カリウム水溶液等のアルカリ性溶液にのみ溶解することが可能であり、これらの水溶液は水溶液中で塩を形成して溶解しているだけであるため、前記アルギン酸カリウム及びアルギン酸ナトリウムと同様に使用できる。 In particular, as alginic acid or a derivative thereof, water-soluble sodium alginate, potassium alginate, ammonium alginate and the like are generally used in large amounts. In the present invention, even these water-soluble alginic acid derivatives can be used as raw materials. Alginate, which does not contain a metal salt, can be dissolved only in an alkaline solution such as an aqueous solution of sodium hydroxide or an aqueous solution of potassium hydroxide, and these aqueous solutions only form a salt in the aqueous solution and dissolve. Therefore, it can be used in the same manner as the potassium alginate and sodium alginate.
分散液としては、水、熱水に不溶であるアルギン酸を用いることができる。アルギン酸は膨潤性及び非膨潤性のものが知られているが、そのいずれも使用することができる。アルギン酸であれば、金属の含有、加熱時にアンモニアが発生する等の問題が生じる恐れがなく、広い用途で適用可能である。 As the dispersion liquid, alginic acid, which is insoluble in water or hot water, can be used. Alginic acid is known to be swellable and non-swellable, and both can be used. Alginic acid can be applied to a wide range of applications without the possibility of causing problems such as metal content and generation of ammonia during heating.
前記溶媒は、中性の水又は金属塩を含まない酸性水溶液であることが特に好ましい。通常、アルギン酸は中性の水又は酸性溶液には溶解しないが、中性の水又は金属塩を含まない酸性の溶媒を用いることで分散液の状態でナノファイバーを製造することができ、金属の含有等を回避できる。金属塩を含まない酸性水溶液としては、例えば、塩酸、酢酸等を挙げることができる。また、具体的には、中性の水又は金属塩を含まない酸性の溶媒としては、ｐＨ９以下（例えば、ｐＨ１〜７）の水溶液を挙げることができる。 The solvent is particularly preferably an acidic aqueous solution containing no neutral water or a metal salt. Normally, alginic acid does not dissolve in neutral water or an acidic solution, but by using an acidic solvent that does not contain neutral water or a metal salt, nanofibers can be produced in the state of a dispersion liquid, and the metal can be produced. It is possible to avoid inclusion and the like. Examples of the acidic aqueous solution containing no metal salt include hydrochloric acid, acetic acid and the like. Specifically, examples of the acidic solvent containing no neutral water or metal salt include an aqueous solution having a pH of 9 or less (for example, pH 1 to 7).
このように、本発明の原料は、前記アルギン酸系ナノファイバーに含まれる多糖類であれば、様々な多糖類（好ましくはアルギン酸又はその誘導体）を用いることができる。例えば、アルギン酸、アルギン酸ナトリウム、アルギン酸カリウム、アルギン酸アンモニウム、アルギン酸カルシウム、アルギン酸プロピレングリコールエステル等の水溶性又は非水溶性のいずれのアルギン酸及びアルギン酸誘導体を使用することができる。これらのアルギン酸及びアルギン酸誘導体は、一種単独で用いることができ、また、二種以上混合して用いることもできる。 As described above, as the raw material of the present invention, various polysaccharides (preferably alginic acid or derivatives thereof) can be used as long as they are polysaccharides contained in the alginic acid-based nanofibers. For example, either water-soluble or water-insoluble alginic acid and alginic acid derivatives such as alginic acid, sodium alginate, potassium alginate, ammonium alginate, calcium alginate, and propylene glycol alginate can be used. These alginic acid and alginic acid derivatives can be used alone or in combination of two or more.
処理を行う際の原料濃度は、混合物全体に対して、０．１〜２０重量％が好ましく、０．２〜１０重量％がより好ましく、０．５〜５重量％が特に好ましい。濃度が０．１重量％以上であれば生産性を向上することができ、濃度が２０重量％よりも低いことでナノファイバー化が進むにつれて高粘度化する可能性及び高粘度化によりナノファイバー化が不完全になる可能性を防ぐことができる。 The raw material concentration at the time of treatment is preferably 0.1 to 20% by weight, more preferably 0.2 to 10% by weight, and particularly preferably 0.5 to 5% by weight, based on the whole mixture. If the concentration is 0.1% by weight or more, the productivity can be improved, and if the concentration is lower than 20% by weight, the viscosity may increase as the nanofiber formation progresses, and the nanofiber formation due to the higher viscosity. Can be prevented from becoming incomplete.
高圧処理を行う時間は、特に限定的ではなく、通常、1分以上（例えば、１分〜２４時間）である。高圧処理は、１回でも、複数回行ってもよい。 The time for performing the high-pressure treatment is not particularly limited, and is usually 1 minute or more (for example, 1 minute to 24 hours). The high pressure treatment may be performed once or a plurality of times.
３．アルギン酸系ナノファイバーを含む分散体
本発明の分散体は、前記アルギン酸系ナノファイバー及び溶媒を含む。溶媒としては、前記製造方法において使用できる溶媒が好ましく、水を含むことが好ましい。
3. 3. Dispersion Containing Alginic Acid-based Nanofibers The dispersion of the present invention contains the alginic acid-based nanofibers and a solvent. As the solvent, a solvent that can be used in the above-mentioned production method is preferable, and water is preferably contained.
本発明の分散体は、処理後の分散体をそのまま用いてもよいが、分散体を濃縮又は希釈することで任意の濃度の分散体とすることができる。また、処理後、分散体をろ過等することで、アルギン酸系ナノファイバーを溶媒と分離し、適宜、分離したアルギン酸系ナノファイバーを溶媒で洗浄した後、再度溶媒に分散させることもできる。洗浄、再度の分散に用いる溶媒は、前記処理で使用する溶媒と同じものを使用することができる。 As the dispersion of the present invention, the treated dispersion may be used as it is, but a dispersion having an arbitrary concentration can be obtained by concentrating or diluting the dispersion. Further, after the treatment, the dispersion can be filtered to separate the alginic acid-based nanofibers from the solvent, and the separated alginic acid-based nanofibers can be appropriately washed with the solvent and then dispersed in the solvent again. As the solvent used for washing and redispersion, the same solvent as that used in the above treatment can be used.
本発明の分散体は、噴霧乾燥することにより、アルギン酸系ナノファイバーを粒径の小さな粒子（好ましくは粒径（Ｄ５０）が２０μｍ以下）として得ることができる。このような粒子は、例えば、樹脂にアルギン酸系ナノファイバーを混練する場合に好適である。 The dispersion of the present invention can be spray-dried to obtain alginic acid-based nanofibers as particles having a small particle size (preferably, the particle size (D50) is 20 μm or less). Such particles are suitable, for example, when kneading alginic acid-based nanofibers into a resin.
以下に、実施例に基づいて本発明をより詳細に説明するが、本発明はこれらの実施例によって限定されるものではない。 Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.
実施例１
アルギン酸（株式会社キミカ製「キミカアシッド」ＳＡ）２０ｇ（図１）に対して水９８０ｇを加え、マグネティックスターラーで10分間混合したところ、不均一な分散液（固形分２重量％）が得られた。その分散液を２４０ＭＰａの圧力でノズルから噴射し、ＳｉＣ（炭化ケイ素）ボールに衝突させるという操作を２０回繰り返したところ、半透明の均一な分散液が得られた。
Example 1
When 980 g of water was added to 20 g (Fig. 1) of alginic acid (“Kimika Acid” SA manufactured by Kimika Co., Ltd.) and mixed with a magnetic stirrer for 10 minutes, a non-uniform dispersion liquid (solid content 2% by weight) was obtained. .. When the operation of injecting the dispersion liquid from a nozzle at a pressure of 240 MPa and causing it to collide with a SiC (silicon carbide) ball was repeated 20 times, a translucent uniform dispersion liquid was obtained.
この分散液のSEM観察により長さ、TEM観察により太さを確認した結果、太さ約１０〜４０ｎｍ、長さは少なくとも３μｍ以上のナノファイバーが観察された（図２，３）。 As a result of confirming the length by SEM observation of this dispersion and the thickness by TEM observation, nanofibers having a thickness of about 10 to 40 nm and a length of at least 3 μm or more were observed (FIGS. 2 and 3).
実施例２
原料をアルギン酸（非膨潤性：和光純薬性）２０ｇ（図４）に変える以外は、実施例１と同様に処理を行った。
半透明の均一な分散液が得られ、この分散液のSEM観察により長さ、TEM観察により太さを確認した結果、太さ約１０〜４０ｎｍ、長さは少なくとも３μｍ以上のナノファイバーが観察された（図５，６）。
Example 2
The treatment was carried out in the same manner as in Example 1 except that the raw material was changed to 20 g of alginic acid (non-swelling: Wako Pure Chemical Industries, Ltd.) (FIG. 4).
A translucent uniform dispersion was obtained, and as a result of confirming the length by SEM observation and the thickness by TEM observation of this dispersion, nanofibers having a thickness of about 10 to 40 nm and a length of at least 3 μm were observed. (Figs. 5 and 6).
実施例３
原料をアルギン酸（膨潤性：和光純薬性）２０ｇ（図７）に変える以外は、実施例１と同様に処理を行った。
Example 3
The treatment was carried out in the same manner as in Example 1 except that the raw material was changed to 20 g of alginic acid (swelling property: Wako Pure Chemical Industries, Ltd.) (FIG. 7).
透明で均一な分散液が得られ、この分散液のSEM観察により長さ、TEM観察により太さを確認した結果、太さ約１０〜４０ｎｍ、長さは少なくとも３μｍ以上のナノファイバーが観察された（図８，９）。 A transparent and uniform dispersion was obtained, and as a result of confirming the length by SEM observation and the thickness by TEM observation of this dispersion, nanofibers having a thickness of about 10 to 40 nm and a length of at least 3 μm were observed. (Figs. 8 and 9).
比較例１
実施例２で用いたアルギン酸（非膨潤性：和光純薬性）２ｇに水９８ｇを加え、マグネティックスターラーで激しく７２時間撹拌した。その結果、均一な状態にはならず、速やかにアルギン酸が沈殿した。
Comparative Example 1
98 g of water was added to 2 g of alginic acid (non-swelling: Wako Pure Chemical Industries, Ltd.) used in Example 2, and the mixture was vigorously stirred with a magnetic stirrer for 72 hours. As a result, the state was not uniform, and alginic acid was rapidly precipitated.
比較例２
実施例２で用いたアルギン酸（膨潤性：和光純薬性）２ｇに水９８ｇを加え、マグネティックスターラーで激しく７２時間撹拌した。その結果、アルギン酸は水を吸収して膨潤し、半透明の状態となったが均一な分散体にはならなかった。
Comparative Example 2
98 g of water was added to 2 g of alginic acid (swelling property: Wako Pure Chemical Industries, Ltd.) used in Example 2, and the mixture was vigorously stirred with a magnetic stirrer for 72 hours. As a result, alginic acid absorbed water and swelled, becoming translucent, but not a uniform dispersion.
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| JP5334055B2 (en) * | 2009-09-14 | 2013-11-06 | 独立行政法人産業技術総合研究所 | Production method of bionanofiber |
| CN102071497B (en) * | 2010-12-03 | 2012-05-09 | 北京化工大学 | Preparation method of sodium alginate nanofiber |
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